Reductive Photocatalytic Proton-Coupled Electron Transfer by a Zirconium-Based Molecular Platform
Metadatos
Mostrar el registro completo del ítemAutor
Jabalera Ortiz, Pedro J.; Perona, Cristina; Moreno Albarracín, Mercedes; Carmona Fernández, Francisco Jesús; Jiménez Gallego, Juan Ramón; Rodríguez Navarro, Jorge Andrés; Garrido Barros, PabloEditorial
Wiley
Materia
Proton-coupled electron transfer photoredox catalysis homogeneous catalysis
Fecha
2024-10-14Referencia bibliográfica
P. J. Jabalera-Ortiz, C. Perona, M. Moreno-Albarracín, F. J. Carmona, J.-R. Jiménez, J. A. R. Navarro, P. Garrido-Barros, Angew. Chem. Int. Ed. 2024, e202411867. https://doi.org/10.1002/anie.202411867
Patrocinador
PID2022- 143153OA-I00 funded by MICIU/AEI/ 10.13039/501100011033; “ERDF/EU”; PID2020-113608RB-I00 funded by MICIU/AEI /10.13039/501100011033; TED2021-129886B-C41 funded by MICIU/AEI /10.13039/501100011033; European Union NextGenerationEU/PRTR; RYC2021-031249-I funded by MICIU/AEI/10.13039/501100011033; PREP2022-000253 funded by MICIU/AEI/10.13039/501100011033; ESF+; Universidad de Granada / CBUAResumen
Reductive proton-coupled electron transfer
(PCET) has important energetic implications in numerous
synthetic and natural redox processes. The development
of catalytic systems that can mediate such transformations
has become an attractive target, especially
when light is used to generate the reactive species
towards solar-to-chemicals conversion. However, such
approach becomes challenged by kinetic competition
with H2 evolution. Here we describe the excited state
reactivity of a molecular Zr-based platform under visible
light irradiation for the efficient reduction of multiple
bonds. Mechanistic investigations shine light on a charge
separation process that colocalizes an excited electron
and an acidic proton to promote selective PCET. We
further leveraged this reactivity for the photocatalytic
reduction of a variety of organic substrates. Our results
demonstrate the promise of this molecular platform to
design strong photocatalytic PCET mediators for reductive
transformations. More broadly, we also show the
potential relevance of PCET mechanisms in the
(photo)redox chemistry of Zr-based molecular materials.